CN112063109A - Nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material and preparation method thereof - Google Patents
Nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material and preparation method thereof Download PDFInfo
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- CN112063109A CN112063109A CN202010954577.1A CN202010954577A CN112063109A CN 112063109 A CN112063109 A CN 112063109A CN 202010954577 A CN202010954577 A CN 202010954577A CN 112063109 A CN112063109 A CN 112063109A
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- volatile oil
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 96
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 96
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 78
- 239000000341 volatile oil Substances 0.000 title claims abstract description 60
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 22
- 235000003261 Artemisia vulgaris Nutrition 0.000 title claims abstract description 20
- 235000003826 Artemisia Nutrition 0.000 title claims abstract description 19
- 244000030166 artemisia Species 0.000 title claims abstract description 19
- 235000009052 artemisia Nutrition 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000001138 artemisia absinthium Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 238000004381 surface treatment Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 241001670235 Artemisia rupestris Species 0.000 claims abstract description 4
- 235000015784 Artemisia rupestris Nutrition 0.000 claims abstract description 4
- 235000001405 Artemisia annua Nutrition 0.000 claims description 15
- 240000000011 Artemisia annua Species 0.000 claims description 15
- 241001249148 Artemisia scoparia Species 0.000 claims description 13
- 235000003069 Artemisia scoparia Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 4
- 235000012830 plain croissants Nutrition 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009849 vacuum degassing Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- XZTUYISAOWDOSC-UHFFFAOYSA-N 1-(4-chlorophenyl)-1,3-dimethylurea Chemical compound CNC(=O)N(C)C1=CC=C(Cl)C=C1 XZTUYISAOWDOSC-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- ZQBVKYZUROTSGX-UHFFFAOYSA-N C(C)O[SiH3].NCCNCCC[Si](OC)(OC)OC Chemical compound C(C)O[SiH3].NCCNCCC[Si](OC)(OC)OC ZQBVKYZUROTSGX-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- BLUAFEHZUWYNDE-NNWCWBAJSA-N artemisinin Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2OC(=O)[C@@H]4C BLUAFEHZUWYNDE-NNWCWBAJSA-N 0.000 claims description 2
- 229960004191 artemisinin Drugs 0.000 claims description 2
- 229930101531 artemisinin Natural products 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 28
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 10
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 241001168877 Artemisia selengensis Species 0.000 description 6
- 235000015759 Artemisia selengensis Nutrition 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 241001055822 Artemisia halodendron Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 235000009051 Ambrosia paniculata var. peruviana Nutrition 0.000 description 1
- 235000003097 Artemisia absinthium Nutrition 0.000 description 1
- 235000017731 Artemisia dracunculus ssp. dracunculus Nutrition 0.000 description 1
- 235000017519 Artemisia princeps Nutrition 0.000 description 1
- 244000065027 Artemisia princeps Species 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000009429 Ginkgo biloba extract Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241001233305 Xanthisma Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxymethyl bisphenol A Chemical compound 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a nano-zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material and a preparation method thereof. The antibacterial material comprises the following components in parts by weight: 10-55 parts of a curing agent; 44-89.6 parts of epoxy resin; 0.2-0.45 parts of artemisia rupestris volatile oil; 0.2-0.45 parts of nano zinc oxide; 0-0.5 parts of an accelerator; the nano zinc oxide is subjected to surface treatment. On one hand, the invention enhances the antibacterial activity by the synergistic effect of the two antibacterial agents and reduces the addition amount of the antibacterial agents; on the other hand, the compatibility of the nano zinc oxide and the epoxy resin is improved, and the mechanical property of the composite material is favorably improved. Meanwhile, the process is simple, green and environment-friendly, only a common epoxy resin molding method is needed, special equipment is not needed, the cost is low, and the large-scale production is facilitated.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-performance antibacterial material and a preparation method thereof, and especially relates to a nano zinc oxide/artemisia yellow wormwood volatile oil/epoxy resin high-performance antibacterial material and a preparation method thereof.
Background
Due to excellent mechanical property, electrical insulation property, processability, dimensional stability, heat resistance and weather resistance, the epoxy resin is widely applied to the fields of electronics and electricity, aerospace, coatings and the like. However, the cross-linked structure of the cured epoxy resin has a certain free volume, so that the cured epoxy resin is easily invaded by moisture, bacteria are bred, the service life of the cured epoxy resin is shortened, and the application field of the cured epoxy resin is limited. Therefore, the research on the antibacterial epoxy resin has important significance and conforms to the sustainable development concept.
In order to achieve the above object, researchers have generally prepared epoxy resins having an antibacterial function by adding an antibacterial agent. The antibacterial agents are various in variety and can be divided into two categories, namely organic antibacterial agents and inorganic antibacterial agents according to different chemical components. Among them, organic antibacterial agents are classified into synthetic antibacterial agents and natural antibacterial agents. The organic synthetic antibacterial agent mainly comprises halogenated matters, phenol and quaternary ammonium salt, although the antibacterial effect is obvious in a short time, the organic synthetic antibacterial agent has the defects of poor durability, easy volatilization, easy decomposition and the like, and is limited by the processing conditions of high polymer materials. The natural organic antibacterial agent is derived from plants or animals, and is environment-friendly and low in cost. For example, patent document CN105368364B discloses an antibacterial epoxy resin potting adhesive based on ginkgo leaf extract and a preparation method thereof, wherein 6-7 parts of natural antibacterial agent is added, and the antibacterial rate of the obtained epoxy resin potting adhesive to escherichia coli and staphylococcus aureus can reach 90%; patent document CN110028762B disclosed before the subject group also reports an antibacterial epoxy resin based on artemisia annua volatile oil and a preparation method thereof, and the antibacterial rate of the obtained epoxy resin composite material on escherichia coli and staphylococcus aureus can reach 90%. Although the epoxy resin based on the natural organic antibacterial agent is green and environment-friendly and has an obvious antibacterial effect, the epoxy resin is large in usage amount on the premise of ensuring high-efficiency antibacterial, and the risk of reducing mechanical properties exists. Inorganic antibacterial agents, especially inorganic nano antibacterial agents, have the advantages of low toxicity, broad spectrum, high efficiency, durability and the like, and for example, nano silver, nano zinc oxide, nano titanium dioxide and the like have attracted wide attention. For example, the subject group reports an epoxy resin composite material based on nano zinc oxide, and the specific method is that the nano zinc oxide is firstly surface-modified, then is dispersed in a curing agent, and then is compounded with epoxy resin (plastic science and technology, 2020,48(03): 25-29). However, the inorganic nano antibacterial agent has poor dispersibility in a polymer matrix, and is easy to agglomerate particularly when the addition amount is large, so that the antibacterial activity and the mechanical property of the material are influenced, and meanwhile, the cost is high, and the large-scale production is limited.
Disclosure of Invention
Aiming at solving the problem that the existing epoxy resin is easy to be corroded by bacteria and overcoming the defects of natural organic antibacterial agents and inorganic nano antibacterial agents in the prior preparation technology of antibacterial epoxy resin, the invention provides a nano zinc oxide/artemisia yellow croissant volatile oil/epoxy resin high-performance antibacterial material and a preparation method thereof. On the basis of the patent CN110028762B, the method considers that the artemisia halodendron volatile oil and the nano zinc oxide are light-color antibacterial agents and have no obvious influence on the color of the product. The nano zinc oxide and the artemisia rupestris volatile oil are compounded, so that on one hand, the antibacterial activity can be enhanced through a synergistic effect, the addition amount of two antibacterial agents is reduced, and the cost is reduced; on the other hand, the nano-zinc oxide after surface treatment can act with hydroxyl and other groups contained in the artemisia scoparia volatile oil, so that the compatibility of the nano-zinc oxide and the epoxy resin is further improved, and the mechanical property of the composite material is favorably improved. Therefore, the natural organic antibacterial agent and the inorganic nano antibacterial agent realize synergistic antibacterial and complementary advantages, and achieve the comprehensive performance index which cannot be realized by a single antibacterial agent.
In order to achieve the purpose, the invention firstly uses silane coupling agent to treat nano zinc oxide powder, then adds the nano zinc oxide after surface treatment into the mixture of artemisia scoparia volatile oil and curing agent, evenly disperses and mixes, then adds into epoxy resin, evenly mixes, defoams in vacuum, pours into a mould, cures and forms at a certain temperature, finally obtains the nano zinc oxide/artemisia scoparia volatile oil/epoxy resin composite material.
The purpose of the invention is realized by the following technical scheme:
the invention provides a nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material which comprises the following components in parts by weight:
10-55 parts of a curing agent;
44-89.6 parts of epoxy resin;
0.2-0.45 parts of artemisia rupestris volatile oil;
0.2-0.45 parts of nano zinc oxide;
0-0.5 parts of an accelerator;
the nano zinc oxide is subjected to surface treatment.
Preferably, the nano zinc oxide is obtained by adopting a silane coupling agent for surface treatment; the surface treatment method comprises the following steps:
dispersing the nano zinc oxide and the silane coupling agent in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 30:1-10:1, then drying in vacuum at the temperature of 100-150 ℃ for 1-3h, cooling and grinding to obtain the nano zinc oxide after surface treatment.
Preferably, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (ethyloxy) silane, and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the curing agent is a substance capable of chemically reacting with epoxy groups in the epoxy resin to form a cross-linked network structure; including anhydride curing agents or amine curing agents.
Preferably, the artemisia selengensis volatile oil comprises volatile oil which is discarded when artemisia selengensis is used for extracting artemisinin.
Preferably, the accelerator is a substance which can accelerate the curing of the epoxy resin and does not influence the material performance; comprises at least one of 2, 4, 6-tri (dimethylaminomethyl) phenol, N-p-chlorophenyl-N, N' -dimethylurea, thiourea or 2-ethyl-4-methylimidazole.
Preferably, the epoxy resin contains two or more epoxy groups and is a substance with good compatibility with the artemisia scoparia volatile oil.
Preferably, the epoxy resin includes at least one of a cycloaliphatic epoxy resin, a bisphenol a type epoxy resin, a glycidylamine type epoxy resin, a bisphenol F type epoxy resin, a glycidylamine type epoxy resin, or a hydroxymethylbisphenol a type epoxy resin.
The invention also provides a preparation method of the nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material, which comprises the following steps:
(1) dispersing nano zinc oxide and a silane coupling agent in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 30:1-10:1, then drying in vacuum at the temperature of 100-150 ℃ for 1-3h, cooling and grinding to obtain nano zinc oxide after surface treatment;
(2) adding 0.2-0.45 part of artemisia scoparia volatile oil into 10-55 parts of curing agent according to the weight parts, uniformly mixing, adding 0.2-0.45 part of nano zinc oxide treated in the step (1) and 0-0.5 part of accelerant, and stirring uniformly;
(3) adding 44-89.6 parts of epoxy resin into the mixture according to the parts by weight, uniformly mixing, carrying out vacuum degassing, pouring into a preheated mold, and curing to obtain the nano zinc oxide/artemisia yellow croissant volatile oil/epoxy resin composite material.
Preferably, in the step (3), the curing conditions are as follows: curing for 2-8h at 30-160 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. in terms of performance, the antibacterial rate of the epoxy resin composite material prepared by the invention to gram-negative bacteria and gram-positive bacteria can reach 90%, and the antibacterial time is long. Compared with a single inorganic nano antibacterial agent, the artemisia halodendron volatile oil is compounded, so that the compatibility between the antibacterial agent and an epoxy resin matrix is effectively improved, and the mechanical property of the composite material is improved; compared with a single natural organic antibacterial agent, the antibacterial performance of the epoxy resin can be greatly improved when the addition amount of the two antibacterial agents is small.
2. In the aspect of preparation process, the preparation method is simple in process, green and environment-friendly, only a common epoxy resin forming method is adopted, no special equipment is needed, the cost is low, large-scale production can be realized, and the waste utilization accords with the sustainable development concept.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron microscope image of a cross section of the nano zinc oxide/artemisia scoparia volatile oil/epoxy resin composite material obtained in example 1;
FIG. 2 is a graph showing the bending strength of a composite material of pure epoxy resin and nano zinc oxide/artemisia scoparia volatile oil/epoxy resin obtained in the example;
FIG. 3 shows the results of the tests of the antibacterial activity of the composite material of nano-zinc oxide/Artemisia princeps Pampanini volatile oil/epoxy resin obtained in example 1 on Escherichia coli, wherein FIG. 3(a) is a control group and FIG. 3(b) is an experimental group;
fig. 4 is a result of an antibacterial performance test of the nano zinc oxide/artemisia selengensis volatile oil/epoxy resin composite material obtained in example 3 on staphylococcus aureus, wherein fig. 4(a) is a control group, and fig. 4(b) is an experimental group.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material, which comprises the following steps:
(1) dispersing nano zinc oxide and gamma-glycidyl ether oxypropyltrimethoxysilane in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 30:1, then carrying out vacuum drying for 2h at 120 ℃, cooling and grinding to obtain nano zinc oxide after surface treatment;
(2) adding 0.45 part of artemisia scoparia volatile oil into 48.8 parts of curing agent (methyl hexahydrophthalic anhydride) according to parts by weight, uniformly mixing, adding 0.25 part of nano zinc oxide prepared in the step (1) and 0.5 part of accelerator (2-ethyl-4-methylimidazole), and stirring until uniform;
(3) adding 50 parts by weight of epoxy resin (alicyclic epoxy resin, model 2021P) into the mixture prepared in the step (2), uniformly mixing, vacuum degassing, pouring into a preheated mold, placing in an oven at 120 ℃ and curing for 4 hours to obtain the nano zinc oxide/artemisia selengensis volatile oil/epoxy resin composite material, wherein an electron microscope scanning image of the section of the nano zinc oxide/artemisia selengensis volatile oil/epoxy resin composite material is shown in figure 1, a bending strength test result is shown in figure 2, an antibacterial performance test result on escherichia coli is shown in figure 3, a control group in figure 3(a) is a blank sample, and an experimental group in figure 3(b) is the composite material prepared in the embodiment.
Tests prove that the antibacterial rates of the prepared nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material to escherichia coli and staphylococcus aureus are 97% and 95% respectively (the antibacterial performance test standard is GB/T21510-.
Example 2
The embodiment provides a preparation method of a nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material, which comprises the following steps:
(1) dispersing nano zinc oxide and gamma-aminopropyltriethoxysilane in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 20:1, then carrying out vacuum drying for 1h at 150 ℃, cooling and grinding to obtain nano zinc oxide after surface treatment;
(2) adding 0.2 part of artemisia scoparia volatile oil into 10 parts of curing agent (dicyandiamide), uniformly mixing, adding 0.2 part of nano zinc oxide prepared in the step (1), and stirring uniformly;
(3) adding 89.6 parts of epoxy resin (bisphenol A type epoxy resin, type E-42) into the mixture prepared in the step (2), uniformly mixing, degassing in vacuum, pouring into a preheated mold, and placing in a 30 ℃ oven for curing for 8 hours to obtain the nano zinc oxide/artemisia yellow croissant volatile oil/epoxy resin composite material, wherein the bending strength test result is shown in figure 2.
Tests prove that the antibacterial rates of the prepared nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material to escherichia coli and staphylococcus aureus are 91% and 90% respectively (the antibacterial performance test standard is GB/T21510-.
Example 3
The embodiment provides a preparation method of a nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material, which comprises the following steps:
(1) dispersing nano zinc oxide and gamma-methacryloxypropyltrimethoxysilane in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 10:1, then carrying out vacuum drying for 3h at 100 ℃, cooling and grinding to obtain nano zinc oxide after surface treatment;
(2) adding 0.25 part of artemisia scoparia volatile oil into 55 parts of curing agent (hexahydrophthalic anhydride), uniformly mixing, adding 0.45 part of nano zinc oxide prepared in the step (1) and 0.3 part of accelerator (2, 4, 6-tris (dimethylaminomethyl) phenol), and stirring uniformly;
(3) adding 44 parts of epoxy resin (hydroxymethyl bisphenol A type epoxy resin, the model is CEQ-45) into the mixture prepared in the step (2) by weight parts, uniformly mixing, vacuum degassing, pouring into a preheated mold, and placing in a 160 ℃ oven for curing for 2 hours to obtain the nano zinc oxide/artemisia xanthium volatile oil/epoxy resin composite material, wherein the bending strength test result is shown in figure 2, the antibacterial performance test result on staphylococcus aureus is shown in figure 4, the control group in figure 4(a) is a blank sample, and the experimental group in figure 4(b) is the composite material prepared in the embodiment.
Tests show that the antibacterial rates of the prepared nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material on escherichia coli and staphylococcus aureus are 94% and 92% respectively (the antibacterial performance test standard is GB/T21510-2008), and the bending strength is 68.3MPa (the bending performance test standard is ASTM D790-2007).
Comparative example 1
The comparative example provides a preparation method of artemisia annua volatile oil/epoxy resin composite material, which is basically the same as the method of example 2, and is different from the method in that: in the comparative example, no nano zinc oxide was added, that is, the treatment of step (1) was not performed, and no nano zinc oxide was added in step (2).
Tests prove that the prepared artemisia selengensis volatile oil/epoxy resin composite material has the antibacterial rates of 84% and 76% on escherichia coli and staphylococcus aureus respectively (the antibacterial performance test standard is GB/T21510-.
Comparative example 2
The comparative example provides a preparation method of a nano zinc oxide/artemisia annua volatile oil/epoxy resin composite material, which is basically the same as the method of the example 1, and is different from the method in that: in this comparative example, the nano zinc oxide was not subjected to the surface treatment, that is, the treatment of the step (1) was not performed, and the nano zinc oxide which was not subjected to the surface treatment was added in the step (2).
Tests show that the antibacterial rates of the prepared nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin composite material on escherichia coli and staphylococcus aureus are 85% and 80% respectively (the antibacterial performance test standard is GB/T21510-2008), and the bending strength is 103.8MPa (the bending performance test standard is ASTM D790-2007).
Comparative example 3
This comparative example provides a method for preparing a nano zinc oxide/epoxy resin composite, which is substantially the same as the method of example 2 except that: in the comparative example, the artemisia scoparia volatile oil is not added, namely the artemisia scoparia volatile oil is not added in the step (2).
Tests prove that the antibacterial rates of the prepared nano zinc oxide/epoxy resin composite material to escherichia coli and staphylococcus aureus are 53% and 45% respectively (the antibacterial performance test standard is GB/T21510-.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A high-performance antibacterial material of nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin is characterized by comprising the following components in parts by weight:
10-55 parts of a curing agent;
44-89.6 parts of epoxy resin;
0.2-0.45 parts of artemisia rupestris volatile oil;
0.2-0.45 parts of nano zinc oxide;
0-0.5 parts of an accelerator;
the nano zinc oxide is subjected to surface treatment.
2. The nano-zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 1, wherein the nano-zinc oxide is obtained by performing surface treatment on a silane coupling agent; the surface treatment method comprises the following steps:
dispersing the nano zinc oxide and the silane coupling agent in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 30:1-10:1, then drying in vacuum at the temperature of 100-150 ℃ for 1-3h, cooling and grinding to obtain the nano zinc oxide after surface treatment.
3. The nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 2, wherein the silane coupling agent is one or more selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (ethyloxy) silane, and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
4. The nano-zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 1, wherein the curing agent is a substance capable of chemically reacting with epoxy groups in the epoxy resin to form a cross-linked network structure; including anhydride curing agents or amine curing agents.
5. The nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 1, wherein the artemisia annua volatile oil comprises volatile oil discarded when artemisia annua is extracted to obtain artemisinin.
6. The nano-zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 1, wherein the accelerator is a substance capable of accelerating the curing of the epoxy resin and not affecting the performance of the material; comprises at least one of 2, 4, 6-tri (dimethylaminomethyl) phenol, N-p-chlorophenyl-N, N' -dimethylurea, thiourea or 2-ethyl-4-methylimidazole.
7. The nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 1, wherein the epoxy resin contains two or more epoxy groups and is a substance with good compatibility with the artemisia annua volatile oil.
8. The nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material according to claim 1 or 7, wherein the epoxy resin comprises at least one of alicyclic epoxy resin, bisphenol a type epoxy resin, glycidyl amine type epoxy resin, bisphenol F type epoxy resin, glycidyl amine type epoxy resin or hydroxymethyl bisphenol a type epoxy resin.
9. The preparation method of the nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material according to claim 1 is characterized by comprising the following steps of:
(1) dispersing nano zinc oxide and a silane coupling agent in a mixed solution of water and absolute ethyl alcohol according to the mass ratio of 30:1-10:1, then drying in vacuum at the temperature of 100-150 ℃ for 1-3h, cooling and grinding to obtain nano zinc oxide after surface treatment;
(2) adding 0.2-0.45 part of artemisia scoparia volatile oil into 10-55 parts of curing agent according to the weight parts, uniformly mixing, adding 0.2-0.45 part of nano zinc oxide treated in the step (1) and 0-0.5 part of accelerant, and stirring uniformly;
(3) adding 44-89.6 parts of epoxy resin into the mixture according to the parts by weight, uniformly mixing, carrying out vacuum degassing, pouring into a preheated mold, and curing to obtain the nano zinc oxide/artemisia yellow croissant volatile oil/epoxy resin composite material.
10. The preparation method of the nano zinc oxide/artemisia annua volatile oil/epoxy resin high-performance antibacterial material as claimed in claim 9, wherein in the step (3), the curing conditions are as follows: curing for 2-8h at 30-160 ℃.
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Effective date of registration: 20231117 Address after: Room 510, Building B, Science and Technology Innovation Park, No. 398 Mahuan Road, Lihai Street, Yuecheng District, Shaoxing City, Zhejiang Province, 312366 Patentee after: Saiweide (Zhejiang) Medical Equipment Co.,Ltd. Address before: 050000 105, building C, Beijing Tianjin Hebei Collaborative Innovation Demonstration Park, No. 769 Taihang street, high tech Zone, Shijiazhuang City, Hebei Province Patentee before: Shijiazhuang Yuanding New Material Co.,Ltd. Patentee before: SHANGHAI JIAO TONG University |